EP1979583B1 - Procédé de fabrication d'une soupape de moteur à explosion, et soupape ainsi obtenue - Google Patents

Procédé de fabrication d'une soupape de moteur à explosion, et soupape ainsi obtenue Download PDF

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EP1979583B1
EP1979583B1 EP07730841A EP07730841A EP1979583B1 EP 1979583 B1 EP1979583 B1 EP 1979583B1 EP 07730841 A EP07730841 A EP 07730841A EP 07730841 A EP07730841 A EP 07730841A EP 1979583 B1 EP1979583 B1 EP 1979583B1
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traces
trace levels
valve
steel
quenching
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EP1979583A1 (fr
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Jacques Montagnon
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Aubert and Duval SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00—Using particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2303/00—Manufacturing of components used in valve arrangements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to iron and steel industry. More specifically, it relates to the manufacture of engine valves.
  • a preferred application of the invention is the manufacture of diesel engine admission valves known as "EGR" (exhaust gases recyling) in which these valves are brought into contact with combustion gases reinjected at the inlet to ensure their complete combustion and the reduction in the amount of polluting discharges.
  • EGR exhaust gases recyling
  • valves When used, these valves can locally reach temperatures of 400 to 500 ° C and are subject to high mechanical stress and a corrosive environment. In addition, the condensates that settle on the valves during the extended shutdown of this type of engine are also very aggressive.
  • US-A-4,741,080 discloses a method for producing a one-piece steel valve, possibly made of austenitic steel, for internal combustion engines, said method comprising a mechanical heat-treatment such as forging extrusion followed by forging, cooling to a air, and a heat treatment.
  • Si% / Mn% Preferably Si% / Mn% ⁇ 1.
  • traces ⁇ Ni ⁇ 0.5% Preferably, traces ⁇ Ni ⁇ 0.5%.
  • traces ⁇ P 0.010%.
  • Said heat or thermomechanical final treatments may include tempering followed by income.
  • Said final heat or thermomechanical treatments may include annealing followed by machining.
  • the parts of the valve concerned by the localized surface hardening may be the end of the stem and / or the seat span.
  • the invention also relates to a one-piece engine-to-explosion valve, characterized in that it was manufactured by the above method.
  • the invention is based first on a precise balancing of the composition of a stainless steel. It makes it possible to provide the manufactured part with a martensitic structure and favorable mechanical properties, as a result of adequate thermomechanical treatments, as well as a corrosion resistance close to that of the austenitic stainless steels. It then relies on heat and mechanical treatments giving the valve its remarkable properties, and in particular localized surface hardening, for example (but not exclusively) HF quenching, of its most stressed parts which finishes the manufacture.
  • the steel used must meet various criteria specific to the application envisaged, namely the manufacture of one-piece valves for internal combustion engines.
  • the volume of metal in the stem and the valve head must have a hardness and a resistance to abrasion not too high considering the range of finishing of the parts (machining, grinding, polishing, ...) and a sufficient ductility .
  • the seat of the valve seat and the end of the stem must have a very high hardness and resistance to abrasion: for this, the steel must be able to respond to a specific surface treatment, namely a quenching. superficial localized.
  • a quenching. superficial localized Such a localized surface hardening is, most conventionally, carried out by a process known as "high frequency quenching" or HF quenching: this operation consists of heating the only zones concerned, using an inductive system, for a short time.
  • the surfaces treated by quenching HF, and whose structure is martensitic easily reach hardnesses of 55 to 60 HRC, which are those required for the intended application.
  • the average hardness sought for wear resistance is most generally 58 HRC.
  • a comparable result can be achieved with other surface treatment processes, such as HF quenching, in a localized surface hardening of the workpiece, such as plasma quenching or laser shock (also known as laser peening).
  • HF quenching in a localized surface hardening of the workpiece, such as plasma quenching or laser shock (also known as laser peening).
  • the steel used in the invention must also fulfill various constraints related to the manufacture of the valve.
  • the manufacture of the valves generally takes place in two main phases, each of which imposes strong constraints on the properties and the behavior of the metal.
  • the metallurgist will first develop, pour and hot shape a steel composition, which he will then deliver to the manufacturer of valves in the form of bars.
  • a first requirement is that the steel used in the invention has a moderate material cost.
  • a low cost material first involves the absence of substantial additions in expensive elements such as nickel, molybdenum, tungsten ... and then the use of low-cost raw materials, currently available on the market and not requiring severe selection. This last point implies that the desired steel can accept the unavoidable residual elements and variable contents (nickel, copper, vanadium, molybdenum %) that are found in the current recycling scrap.
  • the metallurgist When developing steel, the metallurgist must still be able to use high efficiency installations (conventional electric furnaces, continuous casting, etc.) and simple and reliable production processes. In the first place, since the "ingot" channel is used by the processor, the steel must be sufficiently “hardenable” so as to avoid the phenomena of "filleting" ingots (superficial cracking during cooling), which are frequently a source of rejects.
  • the steel should ideally have good malleability properties at high temperatures and the lack of sensitivity to hot crack formation.
  • a low quenchability of the steel is an advantage when the transformation range comprises several intermediate stages of rolling or forging. In fact, a low quenchability limits the risk of intermediate products being broken, by favoring softening of the steel by a self-annealing mechanism during return to ambient temperature.
  • the manufacturer first shears the bars and then performs the actual operation of forming the hot valves, either by forging or by extrusion.
  • the first shearing operation assumes that the metal is not fragile, that its hardness is low and that it offers a non-abrasive behavior with respect to shearing tools.
  • coarse carbides in steel shearing are a source of deterioration of the edge of the shears, and should therefore be avoided.
  • the metal must offer good malleability at these temperatures.
  • valve stem since the valve stem is generally slightly deformed during this operation, its structure is largely dependent on the structure of the initial bar, and especially its evolution during the heating cycle before shaping the valve.
  • the structure of the steel must therefore have a high stability with respect to heating at high temperatures (1150-1200 ° C).
  • the martensitic stainless steels known from the prior art can be classified into two categories, the first consisting of steels with a low carbon content (C ⁇ 0.1%), and the second of steels with a high carbon content ( up to about 1%).
  • Stainless steel low carbon martensitic steels can typically contain up to 17% of chromium and offer good corrosion resistance, which would be compatible with the preferred application envisaged for the invention.
  • these steels are very tempering, sensitive to taps and difficult to respond to annealing treatments that aim to lower the hardness.
  • their maximum hardness in HF quenching does not reach the required levels, while their low carbide content is a limitation to their resistance to abrasion.
  • the high-carbon stainless steel martensitic steels known in the prior art offer good resistance to abrasion, especially better than the carbide content increases, and hardness levels in the rough state of HF quenching which regularly grow with the carbon content.
  • carbon-alloy steels have their hardness increasing with the carbon content. A minimum carbon content of 0.45% is required to provide a minimum hardness of 58 HRC to the raw quenched steel.
  • the quenchability of the martensitic stainless steels of the prior art is not adapted to the range and the manufacturing lines of the valves.
  • steels heavily loaded with chromium and containing about 0.5% or more of carbon offer high quenchability unnecessary or even unwanted because it involves adding annealing cycles in the manufacturing range.
  • X85CrMoV 18-2 steel which is used for highly stressed intake valves and requires high heat resistance, contains a lot (2 to 3%) of molybdenum, which is an expensive component. It is characterized by a high hardenability which is the cause of strong constraints of thermomechanical origin or resulting from the martensitic transformation, and rejects during the manufacture of intermediate products by the steelmaker and the transformer (blacksmith or laminator).
  • silicon plays a key role in achieving and adjusting all the properties and behaviors required of steel.
  • silicon controls the quenchability of the structure.
  • martensitic stainless steels are classified as “self-quenching" steels, that is to say that the martensitic transformation of their structure is very easily obtained during cooling from a temperature in their domain of austenization. Indeed, for moderate carbon contents, the austenite of these steels, formed at high temperature, can be cooled down to low temperatures, for example 250 ° C, without being the seat of any structural transformation: it is in a metastable state. If the cooling is continued, the metastable austenite is transformed rather abruptly into martensite, from a temperature Ms, characteristic of each steel.
  • a high quenching power is attractive at the finished product stage, when one seeks to obtain high mechanical properties by heat treatment of the steel, but is generally a source of multiple problems throughout the manufacturing range of the products.
  • the steel compositions used in the invention which are typical of the stainless steel martensitic steels of the Fe-Cr-C system, nevertheless offer a relatively moderate quenchability, just adapted to small finished products, such as engine valves. explosion. It is the addition of a silicon content greater than 1% which gives them this property.
  • the inventors have discovered that silicon causes the stable precipitation of carbide (Fe, Cr) 7 C 3 over a wide range of austenization temperatures when its content is greater than 1%, as illustrated in FIG. figure 1 which represents a pseudo-binary cut, as a function of the silicon content, of the phase diagram of a steel composition according to the invention.
  • Table 1 Composition of the samples tested Elements (% by weight) VS Yes mn Or Cr MB V NOT W Nb Cu Co al Ti S P A (reference) 0.55 0.43 0.45 0.09 15.5 0.3 0.31 0.12 ⁇ 0.02 ⁇ 0.01 0,022 0.018 ⁇ 0.025 ⁇ 0.010 0.0016 0.0079 B 0.55 1.45 0.52 0.09 15.7 0.3 0.39 0.12 ⁇ 0.02 ⁇ 0.01 0,022 0.018 ⁇ 0.025 ⁇ 0.010 0.0018 0.0082
  • the two castings have a C + N content of 0.67%, close to the maximum limit of the invention (0.70%).
  • the martensitic or bainitic conversion rate of the composition A remains always very high for all the imposed cooling rates, which correspond to air cooling of the core of bars of diameters of between 25 and 200 mm. This material will therefore be sensitive to the formation of taps at various stages of its shaping.
  • the composition B enriched in silicon according to the invention is rapidly transformed at high temperature (between 700 and 800 ° C.), according to a decomposition of the austenite into ferrite, carbides and nitrides.
  • the decomposition of the austenite of this silicon-rich steel strongly resembles the classical pearlitic transformation of carbon steels.
  • the residual rate of martensitic transformation is negligible for all the cooling rates corresponding to an air cooling at the core of bars of diameters greater than or equal to 50 mm, and remains limited to the core. 25mm diameter.
  • the full martensitic transformation of the composition B of the invention remains possible by applying a high cooling rate.
  • the steel B structure is martensitic and has a hardness of 58 HRC. It is, moreover, considerably finer and homogeneous than that of steel A.
  • it is the carbides (Fe, Cr) 7 C 3 which are present in the steel B, whereas it is the carbides (Fe, Cr) 23 C 6 which are present in the steel AT.
  • Carbon is the essential element for imparting its hardness to martensite, or possibly to bainite, formed during quenching. Its minimum content must be 0.45% to reach a hardness of 58 HRC after heat treatment, but also to achieve a metallurgical structure free of delta ferrite.
  • Silicon is a major addition element of the invention. In order to obtain the desired low quenchability, its content must be greater than 1%, preferably greater than 1.4%. It is limited to a maximum of 2.5%, so as to maintain a stable ferrite-free structure. Silicon offers a second very favorable action for the use of steel by reinforcing its resistance to oxidation and corrosion by sulfur: it completes the action of chromium. It is also an efficient and inexpensive deoxidation element. However, silicon lowers the melting temperature (solidus) of the steel, which reduces the forgeability range.
  • the maximum silicon content will be limited to 2% when looking for the best malleability at high temperature, up to 1200 ° C.
  • Chromium is an essential element of the steel used in the invention and allows its protection vis-à-vis the environments of the intake valve. These, in diesel engines with exhaust gas re-injection, are constituted in operation by hot oxidizing gases, and possibly sulphurous depending on the sulfur content in the fuel. The condensates of these gases are also corrosive.
  • the chromium oxide that forms on the surface of the steel is truly continuous and protective only for a minimum average content in the steel matrix of 12%. It is therefore considered that this value is the minimum content of chromium within the scope of the invention. In view of the fact that the carbon present in the steel fixes a fraction of the chromium, and that this fraction is therefore no longer available for the formation of the oxide film, the minimum content of chromium in the composition is, however, preferably 14%.
  • the maximum chromium content is dictated by the metallurgical equilibrium of the steel and, in particular, by the desire to obtain a purely austenitic, ferrite-free matrix structure at the heat treatment and heat transformation temperatures. Without the addition of nickel, which maintains the austenitic structure but is also expensive, and in the presence of carbon + nitrogen contents of 0.55 to 0.70% as required by the invention, the maximum permissible content of chromium is 18%. As a consequent addition of silicon is practiced in the invention, and since this element has an effect similar to chromium, that is to say, it favors the appearance of the ferritic phase, the maximum chromium content is preferably limited to 16%. Beyond this, there is a risk of occurrence of delta ferrite when the contents of Si are high and the contents of C + N low.
  • Nitrogen addition is practiced up to a maximum content of 0.15%, preferably up to 0.12%, so as not to exceed the maximum solubility of this element during solidification. This would lead to the formation of gas bubbles in the metal, resulting in the appearance of pores (blisters) on the solidified metal.
  • Inexpensive nitrogen is used as a carbon additive for two reasons.
  • nitrogen is beneficial to the corrosion resistance of steel in the presence of corrosive condensates.
  • the minimum nitrogen content is 0.05%, and must be such that C + N ⁇ 0.55% so as to achieve the correct composition balance (absence of delta ferrite). It must be such that C + N ⁇ 0.70% so that the maximum levels of carbon and nitrogen as defined above are not exceeded.
  • Vanadium addition is practiced to form nitride and vanadium carbide precipitates with nitrogen and carbon which are stable at the heat treatment temperatures. This makes it possible to limit the magnification of the grain of the structure at these temperatures, where a recrystallization of the metal transformed by rolling or forging occurs.
  • Vanadium nitrides and carbides are favorable for the abrasion resistance of steel, and are also known to increase the creep resistance of martensitic steels.
  • vanadium nitride VN makes it possible to limit that of chromium nitride Cr 2 N which depletes the matrix of chromium.
  • molybdenum may also be practiced for its effect, known from the prior art, which is to help limit the brittleness of steel treated for high hardness.
  • a significant effect begins to exist from 0.2%.
  • a maximum content of 0.5% is allowed not to unnecessarily increase the material cost of steel.
  • These materials may also contain other residual elements, not essential to the properties of the steel used in the invention, and may therefore be present only in the form of traces.
  • the residual metallic elements that are most often found in the loads resulting from steels to be recycled are essentially manganese, nickel, copper, tungsten, niobium and, more rarely, cobalt.
  • Manganese is present in most ferrous raw materials that can be found on the market. It is an easily oxidizable element in furnaces such as the electric arc furnace, but its deliberate and thorough elimination during processing can be costly, and it is not useful in the invention.
  • the recycling charges can usually contain up to 2%, which is tolerable within the scope of the invention, and a large fraction is lost anyway by oxidation during production: it is therefore easy to contain the final manganese content less than 1% in the steels used in the invention, through a judicious choice of a mixture of raw materials suitable for conducting the development of steel in the furnaces of steel mills.
  • manganese can be harmful at levels greater than 2% since it is known, in general, to reduce the resistance to oxidation and sulfurization, to stabilize the austenite and to increase the martensitic hardenability of the steels. Its maximum residual content should therefore be contained at less than 2% and, preferably, between traces and 1%, which is easy and inexpensive for the steelmaker.
  • the steel used in the invention contains levels of manganese and silicon such that their Si / Mn% ratio is greater than or equal to 1, since this condition promotes the flowability of the liquid metal in the casting refractories in the presence a natural atmosphere.
  • Nickel is increasingly present in ferrous raw materials recycling: thus, it is common to find it in proportions of 0.2 to 0.4%. Unlike manganese, the nickel of the raw materials is little oxidized during production, for example in conventional electric arc furnaces. It will therefore be almost completely in the final metal.
  • the steel used in the invention is an element which greatly increases the quenchability and which is, as such, undesirable at levels greater than 1%.
  • it will be contained at most between traces and 0.5%.
  • Copper like nickel, is also present in the common ferrous raw materials of recycling, at levels of about 0.1 to 0.2%, even up to 0.4%, and is not eliminated during the elaboration. Copper is known to degrade the forgeability of iron-chromium steels, because it promotes the forming a liquid film in the grain boundaries of the steels when they are brought to the very high temperatures of the thermomechanical transformation range. It is also known that nickel very effectively combats this intergranular "liquefying" mechanism by stabilizing the austenite phase to the detriment of the liquid phase. If nickel is significantly present, the steel used in the invention can therefore tolerate a relatively high copper content.
  • Cobalt can exceptionally be found in certain specific raw materials. Like nickel, it is slightly oxidizable during processing in conventional electric arc furnaces. However, unlike nickel, cobalt has no adverse effect on the properties and behavior of the valves of the invention.
  • the steel composition used in the invention can therefore comprise up to 1% cobalt, in the form of a residual element.
  • Niobium is known to form, at very low levels, stable carbides and nitrides which contribute, in steels, to limiting the magnification of the austenitic grain at the austenization or thermomechanical transformation temperatures. Niobium can therefore effectively complement the role of vanadium for the control of grain size in the steel used in the invention. But niobium is also known to promote the precipitation of eutectic carbides and nitrides in a weakening network during solidification. steel ingots. For these reasons, the niobium content of the steel used in the invention is limited to 0.15%.
  • this element can, in some cases, bring strong cohesion to the grain boundaries. If it is desired to add thereto, which is in no way indispensable in the context of the invention, its content must be between traces and 0.0050%, preferably between traces and 0.0020%.
  • Aluminum and titanium are to be avoided because they form with nitride weakening nitrides, therefore undesirable.
  • the aluminum content should be ⁇ 0.025%, preferably ⁇ 0.015%.
  • the titanium content must be ⁇ 0.010%.
  • the invention has no particular requirements. Unless particularly good inclusion cleanliness is desired, one is content with the oxygen content naturally resulting from the silicon content (which is generally the predominant deoxidizing element) and the conditions of preparation necessary to obtain the desired levels for the other elements. An oxygen content of the order of 0.0050% or even less can be commonly obtained, but is not imperative in the general case, because the mechanical properties which are primarily to be optimized in the context of the invention depend little on the inclusion cleanliness.
  • the steels used in the invention can be prepared according to the methods applicable to common materials, taking into account their particularities. Thus, they can not be developed under vacuum because it is necessary to practice a nitrogen addition in gaseous form.
  • an electric furnace, or an AOD reactor, or any other means suitable for the production of steels containing high levels of nitrogen may be used, including secondary refining processes by electroslag remelting.
  • the remelting can be done, for example, slag with consumable electrode if one is looking for a high inclusion cleanliness.
  • the casting of the metal takes place either by ingots or by continuous casting.
  • a homogenizing heat treatment of the solidification structures is feasible, if necessary, at temperatures of between 1150 and 1225 ° C.
  • a heat-thermomechanical transformation stage of the cast half-product for example a forging and / or rolling, at temperatures typically between 1000 and 1200 ° C.
  • An annealing is optionally applicable after the hot transformation, if it is desired to soften the structure as much as possible for operations at ambient temperature such as straightening of the bars, machining.
  • the softening of the products is possible by means of isothermal softening annealing at temperatures between 650 and 900 ° C, for periods of 2 to 8 hours, followed by cooling in the air or in the oven at the rate of cooling the oven.
  • localized surface quenching is carried out, for example HF quenching or any other process giving comparable results in areas of high hardness: the seat of the valve seat and / or the end of the stem.
  • the bars were then annealed for 8 hours at 880 ° C and then cooled in the oven to 550 ° C, at which temperature the bars were taken out of the oven and cooled in air.
  • the hardness of the bars after this softening was then low: 235 HB, or about 22 HRC (the HRC measurement having, at this low level of hardness, greater significance).
  • the hardenability limit for air cooling was 40 mm.
  • the hardness of the bainitomensitic structure was 58.5 HRC. .
  • Table 2 shows examples of income conditions and HRC hardnesses that can be obtained on the previous bars.
  • Table 2 HRC hardnesses obtained on steel C according to income conditions. Temperature / time / cooling income hardness HRC 500 ° C / 2h / Air 57.1 525 ° C / 2h / Air 54.4 550 ° C / 2h / Air 47.4 575 ° C / 2h / Air 44.0 600 ° C / 2h / Air 41.1 625 ° C / 2h / Air 39.5 650 ° C / 2h / Air 37.5 700 ° C / 2h / Air 33.1 750 ° C / 2h / Air 29.4 800 ° C / 2h / Air 24.6
  • HF quenching has been performed on the end of the stem and / or the seat of the valve seat, to generally give them a hardness of 55 to 60 HRC.
  • Another example of treatment according to the invention is the following:
  • the cast ingot was homogenized for 8 hours at 1120 ° C, then forged with a pestle into a 17 mm square section bar at a temperature of 1180 ° C.
  • the bars were baked in an oven at 650 ° C, for a period of 2 hours, for a metal softening treatment by post-forging isothermal annealing.
  • the metal was tested by the "fast" tensile test at the strain rate of 85 mm / s and at temperatures between 1000 and 1230 ° C, in order to assess its malleability in the field. thermomechanical transformation temperatures.
  • the malleability of the metal is described by the usual parameters of the tensile test, ie the elongation at break (A%) and the section reduction at the fracture level (Z%).
  • the hot resistance is represented by the maximum stress rupture variable (Rm Mpa).
  • composition D the sum of the C + N contents of which is situated at the lower limit of the values according to the invention, the martensitic conversion rate, measured as a result of dilatometry tests conducted at various cooling speeds since the temperature of d austenitization of 1050 ° C, becomes negligible for all cooling rates less than or equal to that corresponding to a natural air cooling in the heart of a bar diameter of about 60mm.
  • the martensite formed after a faster cooling from 1050 ° C has a hardness of 57.7 HRC.
  • This steel E is thus a high carbon chromium-molybdenum martensitic stainless steel of the type X85CrMoV 18-2 previously cited.
  • the metal comes from an ingot of about 1.5 tons of industrial casting. This ingot was homogenized at the temperature of 1170 ° C., and then was rolled to the raw diameter 90 mm, starting from this temperature. In addition, the bar used for the test was treated by isothermal annealing at 830 ° C, for softening before peeling and cutting.
  • this steel has a marked maximum in a range of limited magnitude between 1120 and 1200 ° C, then drops sharply.
  • This steel is therefore significantly less tolerant than steel D at variations in the processing conditions. Above all, in the absolute, its malleability is much lower than that of steel D, its maximum values of A% and Z% being much lower than those of steel D.
  • this reference steel E responds significantly less to the technical problems posed than the steels used in the context of the invention.

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  • Chemical & Material Sciences (AREA)
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  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
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  • Heat Treatment Of Steel (AREA)
EP07730841A 2006-01-26 2007-01-22 Procédé de fabrication d'une soupape de moteur à explosion, et soupape ainsi obtenue Active EP1979583B1 (fr)

Priority Applications (1)

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PL07730841T PL1979583T3 (pl) 2006-01-26 2007-01-22 Sposób wytwarzania zaworu do silnika z zapłonem i uzyskany w ten sposób zawór

Applications Claiming Priority (2)

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FR0600724A FR2896514B1 (fr) 2006-01-26 2006-01-26 Acier martensitique inoxydable et procede de fabrication d'une piece en cet acier, telle qu'une soupape.
PCT/FR2007/000121 WO2007085720A1 (fr) 2006-01-26 2007-01-22 Procédé de fabrication d'une soupape de moteur à explosion, et soupape ainsi obtenue

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BR (1) BRPI0706849A2 (es)
ES (1) ES2367452T3 (es)
FR (1) FR2896514B1 (es)
PL (1) PL1979583T3 (es)
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WO (1) WO2007085720A1 (es)

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UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
KR20160122804A (ko) * 2014-02-18 2016-10-24 우데홀름스 악티에보라그 플라스틱 몰드용 스테인리스 강 및 스테인리스 강으로 만들어지는 몰드
BR102014016213A2 (pt) * 2014-06-30 2016-02-10 Mahle Int Gmbh válvula para motores de combustão interna e processo para obtenção de uma válvula
ES2643579T3 (es) * 2014-12-09 2017-11-23 Voestalpine Precision Strip Ab Tira de acero inoxidable para válvulas de aleta
US9890436B2 (en) 2014-12-09 2018-02-13 Voestalpine Precision Strip Ab Stainless steel strip for flapper valves
CN104561757A (zh) * 2014-12-31 2015-04-29 铜陵市经纬流体科技有限公司 一种硼强化珠光体软密封闸阀阀体及其制备方法
WO2016174500A1 (fr) * 2015-04-30 2016-11-03 Aperam Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit
CN105018844B (zh) * 2015-08-21 2017-02-01 武汉钢铁(集团)公司 低成本高韧性超级耐磨钢及其制备方法
CN106884077B (zh) * 2017-01-18 2021-02-23 抚顺特殊钢股份有限公司 一种高温合金冷拉材两段式电淬火软化退火工艺
DE102017003965B4 (de) * 2017-04-25 2019-12-12 Zapp Precision Metals Gmbh Martensitischer Chromstahl, Stahlfolie, perforierte und/oder gelochte Komponente aus einer Stahlfolie, Verfahren zum Herstellen einer Stahlfolie
BR112021024509A2 (pt) * 2019-06-05 2022-01-18 Ab Sandvik Materials Tech Uma liga de aço inoxidável martensítico
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CN111172471B (zh) * 2020-02-18 2021-02-26 北京科技大学 一种冰球冰刀材料的制备方法

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TWI403595B (zh) 2013-08-01
EP1979583A1 (fr) 2008-10-15
JP5296554B2 (ja) 2013-09-25
TW200745350A (en) 2007-12-16
ATE515626T1 (de) 2011-07-15
JP2009524740A (ja) 2009-07-02
BRPI0706849A2 (pt) 2011-04-12
US9181824B2 (en) 2015-11-10
US20090301615A1 (en) 2009-12-10
FR2896514B1 (fr) 2008-05-30
PL1979583T3 (pl) 2011-11-30
AR059191A1 (es) 2008-03-12
WO2007085720A1 (fr) 2007-08-02
ES2367452T3 (es) 2011-11-03
FR2896514A1 (fr) 2007-07-27

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